WO2007011401A2 - Conducteurs electroniques et ioniques mixtes, composites, a l'oxyde, pour la separation de l'hydrogene - Google Patents
Conducteurs electroniques et ioniques mixtes, composites, a l'oxyde, pour la separation de l'hydrogene Download PDFInfo
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- WO2007011401A2 WO2007011401A2 PCT/US2005/038081 US2005038081W WO2007011401A2 WO 2007011401 A2 WO2007011401 A2 WO 2007011401A2 US 2005038081 W US2005038081 W US 2005038081W WO 2007011401 A2 WO2007011401 A2 WO 2007011401A2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/0271—Perovskites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0073—Sealings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
- C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0681—Reactant purification by the use of electrochemical cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
- H01M8/0687—Reactant purification by the use of membranes or filters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0053—Hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Definitions
- FIG. 2 is a schematic illustration of an apparatus for hydrogen separation according to one or more embodiments of the invention.
- FIG. 5 is an SEM micrograph of a polished surface of a GDC/YSTA composite according to one or more embodiments of the present invention.
- FIG. 7 is an Arrhenius plot of the total conductivity of a GDC/YSTA composite in a reducing environment (7 x 10 "18 atm O 2 ).
- FIG. 8 shows the total conductivity of a GDC/YSTA composite membrane over a range of oxygen partial pressures.
- FIG. 9 is a plot of a typical conductivity relaxation transient for a
- Electroneutrality is preserved in the case of transfer of oxygen ions and electrons when the transfer of oxygen ions is opposite in direction to transfer of electrons. In the case of oxygen ions and electron-holes, transfer of both species is in the same direction to preserve electroneutrality. If the hydrogen purification reaction is reconfigured, with steam being used on both sides of the membrane (i.e. mixtures of syn gas (or other hydrocarbon reformate) and steam on one side and pure steam on the other side), the reactions are:
- the gases exiting the steam side of the membrane contain a mixture of hydrogen and remnant water vapor. The water vapor present in this stream can be condensed to result in a stream of pure hydrogen.
- MIEC membranes used here are thermally and chemically stable under conditions typically encountered in membrane separation of hydrogen, i.e., p 02 in the range of about 10 "7 -10 "20 or about 1CT 16 -1O ⁇ 20 on at least one side of the membrane and temperatures generally above 500°C, usually about 700- 1000 0 C.
- both the high oxygen ion conductive phase and the high electronic conductive phase of the MIEC membrane system are individually stable in the gas atmospheres and temperatures prevailing on both sides of the membrane during the hydrogen separation process.
- These membranes are typically gas impermeable and separate components on the basis of ionic conductivity characteristics, not on the basis of molecular size. Their thickness generally ranges from about l ⁇ m to about 3 mm.
- the membrane includes an oxygen ion conducting phase having a high oxygen ion conductivity.
- the oxygen ion conducting phase may have, but is not required to have, a low electronic conductivity of about 0.01 S/cm to about 1.0 S/cm, or about 0.01 S/cm to about 0.2 S/cm.
- the membrane includes an electronic phase having a high electronic conductivity, e.g., greater than about 1.0 S/cm or about 5 S/cm to about 100 S/cm, or about 10 S/cm to 30 S/cm.
- the electronically conducting phase may have, but is not required to have, a low ion conductivity.
- the electronic conductivity is not the limiting transport factor in the membrane.
- the oxygen ion-conducting materials or phases may be an oxygen ion conductive mixed metal oxide having a fluorite structure.
- the oxygen ion conducting material may be a doped fluorite compound.
- the higher ionic conductivity is believed to be due to the existence of oxygen ion site vacancies.
- One oxygen ion vacancy occurs for each divalent or each two trivalent cations that are substituted for a tetravalent ion in the lattice.
- Any of a large number of oxides such as rare earth doped zirconia-, ceria-, hafnia-, or thoria-based materials may be used.
- Some of the known solid oxide transfer materials include Y 2 ⁇ 3-stabilized ZrO 2 , CaO-stabilized ZrO 2 , Sc 2 O 3 - stabilized ZrO 2 , Y 2 O 3 -stabilized CeO 2 , CaO-stabilized CeO, GaO-stabilized CeO 2 , ThO 2 , Y 2 O 3 -stabilized ThO 2 , or ThO 2 , ZrO 2 , CeO 2 , or HfO 2 stabilized by addition of any one of the lanthanide oxides or CaO. Additional examples include strontium- and magnesium-doped lanthanum gallate (LSGM). Many other oxides are known which have demonstrated oxygen ion-conducting ability which could be used in the multiphase mixtures, and they are included in the present concept.
- LSGM strontium- and magnesium-doped lanthanum gallate
- a dual phase membrane includes an oxygen ion conductor such as a rare earth doped ceria, e.g., RE 2 O 3 -CeO 2 , where RE is a rare earth metal, e.g., Y, Gd, Sm, La, Yb, etc., and an n-type electronic conductor such as donor doped strontium titanate, e.g., R x Sr 1-x TiO 3- ⁇ , where R is a trivalent ion doping for Sr such as Gd, Y, La, Nd, Al etc.
- an oxygen ion conductor such as a rare earth doped ceria, e.g., RE 2 O 3 -CeO 2
- RE is a rare earth metal, e.g., Y, Gd, Sm, La, Yb, etc.
- an n-type electronic conductor such as donor doped strontium titanate, e.g., R x Sr 1-x TiO 3- ⁇
- the membranes used are generally bi-directional and that transfer of a component across the membrane is a function of concentration of that component on both sides of the membrane.
- FIG. 2 A larger scale apparatus is shown in FIG. 3.
- the membrane 30 is sealed between cut ends of two alumina tubes (31 and 32). Between the membrane and the ends of the tubes is placed an o-ring 35 for sealing the membrane to the tubes. This frequently is a gold o-ring that melts and forms the seal.
- a smaller diameter tubes 33 is inserted into the reformate gas side of the membrane (which is closed from the atmosphere with a stainless steel manifold 37) to carry the reformate gas to the membrane, while the purified hydrogen gas is removed from the opposite side of the membrane via another tubes 34.
- the entire apparatus is heated to 800-lOOOC with furnace heating elements 36.
- syn gases can be generated by using the steam methane reformation (SMR) process, in which the following reaction takes place:
- GDC and YSTA powders were synthesized by conventional powder processing using Gd 2 O 3 , CeO 2 , Y 2 O 3 , SrCO 3 , TiO 2 , and Al 2 O 3 (Alfa Aesar) as precursor materials.
- the GDC and YSTA powders were prepared by calcination of stoichiometric mixtures of precursor materials at 1300 0 C for 4 h. The calcined products were then finely ground for 24 h using a ball mill.
- the mean particle size of the milled powders was 2 and 4 ⁇ m for the GDC and YSTA phases, respectively, as evaluated using a Horiba LA-910 laser light scattering analyzer.
- the fine powders were then mixed in the volume ratio of 40% GDC-60% YSTA based on the density values of GDC and YST available in the literature.
- the particulate composite mixture was then milled in methanol for 24 h and then dried to remove the organics.
- the dried composite mixture was pressed into a disk 35 mm diameter and 2.5 mm thick at a pressure of about 500 kg/cm 2 .
- the disk was first sintered in air at 1500°C for 4 h, cooled, and then resintered in a reducing atmosphere at an oxygen partial pressure of IO 48 atm at 1400°C for 4 h.
- the heating and cooling rates for the sintering steps were fixed at 5°C/min.
- the density of the sintered pellet was 5.99 g/cm , which is close to the calculated density of 6.00 g/cm using the theoretical densities of GDC and doped SrTiO 3 .
- the composite phase stability was determined by X-ray diffraction (XRD) analysis (using a Rigaku 18KW diffractometer with Cu Ka radiation (copper anode)) as is shown in FIG. 4.
- trace (a) and trace (b) are XRD traces obtained from single phase powders of GDC and YSTA
- trace (c) is the XRD trace of a physical mixture of GDC and YSTA
- trace (d) is a sintered composite of GDC and YSTA.
- the traces and in particular, trace (d) show that the GDC and YSTA phases retain their original fluorite and perovskite structures, respectively, and do not form any derivative phases.
- GDC and YSTA do not react with each other and a fine GDC/YSTA composite is obtained.
- FIG. 5 An SEM image of the polished surface of the composite membrane sintered in air at 1500 0 C for 4 h and subsequently resintered under reducing conditions at 1400 0 C for 4 h at an oxygen partial pressure of less than 10 " is shown in FIG. 5.
- the grain sizes are in the range of 3-6 ⁇ m, which plays a positive role in conductivity.
- the small grain size provides good mechanical properties, while the large grain boundaries are not good for conductivity.
- the two phase materials are well-percolated, which is important from the standpoint of achieving high ambipolar conductivity.
- Elemental composition of the pellet was determined using wavelength dispersive spectrometers (WDS) on an electron microprobe.
- WDS wavelength dispersive spectrometers
- FIG. 6 four locations within the sample where the composition was measured using WDS are shown. Points 1 and 3 are located within the YSTA system and points 2 and 4 are located within the GDC system.
- the WDS results for GDC and YSTA phases in the composite sample indicated good agreement between intended and experimentally determined compositions.
- the measured composition inside the grains suggested some interdiffusion of rare-earth elements (Gd, Y) across the two-phase boundaries.
- Y and Gd are both trivalent rare-earth cations with closely matched ionic radii. The interdiffusion is not expected to have a significant detrimental effect on the transport properties of the composite.
- GSTA Gd-doped SrTiO 3
- FIG. 8 shows the total conductivity of the composite membrane over a range of oxygen partial pressures.
- the membrane materials exhibits a total conductivity in the range of 2-6 S/cm over a range of oxygen partial pressures that prevail during the hydrogen gas separation process.
- the large measured values for the oxygen chemical diffusion coefficient at lower oxygen partial pressures indicate that the two phases are percolative.
- the ionic conductivity of GDC at the high oxygen partial pressures (ca 10 "10 atm) is about 0.2 S/cm.
- the measured total conductivity is about 2 S/cm under these conditions and a large portion of the total conductivity is electronic conductivity from the YSTA phase.
- Arrhenius plots of D (chemical diffusion coefficient) and K ex (surface exchange coefficient) are shown in FIG. 10.
- D and K 6x have values around 10 "5 cm 2 /s and 10 "4 cm/s, respectively.
- the chemical diffusion coefficient and surface exchange coefficient are similar in magnitude to single phase perovskites such as LSCF and LCF under oxidizing conditions.
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Abstract
L'invention concerne une membrane à conduction électronique et ionique mixte comprenant un composite en céramique à l'état solide, diphasique, la première phase comprenant un conducteur d'ions oxygène et la seconde phase comprenant un oxyde conducteur d'électrons de type n. Cet oxyde conducteur d'électrons est stable à une pression partielle de l'oxygène aussi basse que 10-20 atm et possède une conductivité électronique d'au moins 1 S/cm. L'invention concerne également un système de séparation d'hydrogène et des procédés associés dans lesquels est utilisé cette membrane à conduction électronique et ionique mixte.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2007543065A JP2008520426A (ja) | 2004-11-23 | 2005-10-21 | 水素分離のためのイオンおよび電子伝導性の酸化物混合複合体 |
EP05858461A EP1814646A2 (fr) | 2004-11-23 | 2005-10-21 | Conducteurs electroniques et ioniques mixtes, composites, a l'oxyde, pour la separation de l'hydrogene |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US63036804P | 2004-11-23 | 2004-11-23 | |
US60/630,368 | 2004-11-23 |
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WO2007011401A2 true WO2007011401A2 (fr) | 2007-01-25 |
WO2007011401A3 WO2007011401A3 (fr) | 2007-04-12 |
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PCT/US2005/038081 WO2007011401A2 (fr) | 2004-11-23 | 2005-10-21 | Conducteurs electroniques et ioniques mixtes, composites, a l'oxyde, pour la separation de l'hydrogene |
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US (1) | US7588626B2 (fr) |
EP (1) | EP1814646A2 (fr) |
JP (1) | JP2008520426A (fr) |
WO (1) | WO2007011401A2 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007148057A1 (fr) * | 2006-06-21 | 2007-12-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Membrane de séparation de l'oxygène |
JP2008247649A (ja) * | 2007-03-29 | 2008-10-16 | Tdk Corp | 複合型混合導電体 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8012380B2 (en) * | 2004-03-05 | 2011-09-06 | Ceramatec, Inc. | Proton conducting ceramic membranes for hydrogen separation |
US20070245897A1 (en) * | 2006-04-20 | 2007-10-25 | Innovene Usa | Electron, hydrogen and oxygen conveying membranes |
JP4748089B2 (ja) * | 2007-03-29 | 2011-08-17 | Tdk株式会社 | 複合型混合導電体 |
US20080248363A1 (en) * | 2007-04-06 | 2008-10-09 | Alfred University | Composite electrolyte material having high ionic conductivity and depleted electronic conductivity and method for producing same |
DE102007037203B4 (de) * | 2007-07-30 | 2009-06-10 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verfahren zur Bestimmung von Diffusions- und/oder Austauschkoeffizienten eines Werkstoffs |
US8118934B2 (en) * | 2007-09-26 | 2012-02-21 | Wang Nang Wang | Non-polar III-V nitride material and production method |
US8652947B2 (en) * | 2007-09-26 | 2014-02-18 | Wang Nang Wang | Non-polar III-V nitride semiconductor and growth method |
US20110263912A1 (en) * | 2007-11-07 | 2011-10-27 | Air Products And Chemicals, Inc. | Control Of Kinetic Decomposition In Mixed Conducting Ion Transport Membranes |
US8876959B2 (en) * | 2007-12-06 | 2014-11-04 | Technion Research and Development Ltd | Self-heated dense ceramic tubes for separating gases |
EP2229702B1 (fr) * | 2007-12-21 | 2012-03-28 | Saint-Gobain Ceramics & Plastics, Inc. | Interconnexion céramique pour empilages de piles à combustible |
KR101096058B1 (ko) | 2009-02-05 | 2011-12-19 | 전남대학교산학협력단 | 복합 기능성 수소 분리막, 이를 포함하는 수소 생산 시스템 및 이들을 이용한 수소 생산방법 |
US8323463B2 (en) * | 2010-01-22 | 2012-12-04 | Praxair Technology, Inc. | Catalyst containing oxygen transport membrane |
SE535245C2 (sv) * | 2010-08-02 | 2012-06-05 | Gett Fuel Cells Internat Ab | Bränsleceller utan ektrolyter |
US9561476B2 (en) | 2010-12-15 | 2017-02-07 | Praxair Technology, Inc. | Catalyst containing oxygen transport membrane |
US9486735B2 (en) | 2011-12-15 | 2016-11-08 | Praxair Technology, Inc. | Composite oxygen transport membrane |
US8795417B2 (en) | 2011-12-15 | 2014-08-05 | Praxair Technology, Inc. | Composite oxygen transport membrane |
JP6046959B2 (ja) * | 2012-09-05 | 2016-12-21 | 日本特殊陶業株式会社 | 酸素透過膜 |
JP2016505501A (ja) | 2012-12-19 | 2016-02-25 | プラクスエア・テクノロジー・インコーポレイテッド | 酸素輸送膜集合体をシールするための方法 |
US9453644B2 (en) | 2012-12-28 | 2016-09-27 | Praxair Technology, Inc. | Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream |
US9611144B2 (en) | 2013-04-26 | 2017-04-04 | Praxair Technology, Inc. | Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion |
US9296671B2 (en) | 2013-04-26 | 2016-03-29 | Praxair Technology, Inc. | Method and system for producing methanol using an integrated oxygen transport membrane based reforming system |
US9938145B2 (en) | 2013-04-26 | 2018-04-10 | Praxair Technology, Inc. | Method and system for adjusting synthesis gas module in an oxygen transport membrane based reforming system |
US9212113B2 (en) | 2013-04-26 | 2015-12-15 | Praxair Technology, Inc. | Method and system for producing a synthesis gas using an oxygen transport membrane based reforming system with secondary reforming and auxiliary heat source |
WO2014201274A1 (fr) | 2013-06-12 | 2014-12-18 | Adam Clayton Powell | Électrodes métalliques liquides améliorées pour la séparation de gaz |
CN106413873B (zh) | 2013-10-07 | 2019-10-18 | 普莱克斯技术有限公司 | 陶瓷氧输送膜片阵列重整反应器 |
US9452388B2 (en) | 2013-10-08 | 2016-09-27 | Praxair Technology, Inc. | System and method for air temperature control in an oxygen transport membrane based reactor |
US20160362805A1 (en) * | 2013-11-01 | 2016-12-15 | Adam Clayton Powell, IV | Methods and apparatuses for increasing energy efficiency and improving membrane robustness in primary metal production |
WO2015084729A1 (fr) | 2013-12-02 | 2015-06-11 | Praxair Technology, Inc. | Procédé et système de production d'hydrogène au moyen d'un système de reformage à base de membrane de transport d'oxygène avec un reformage secondaire |
WO2015123246A2 (fr) | 2014-02-12 | 2015-08-20 | Praxair Technology, Inc. | Procédé à base de réacteur à membrane de transport d'oxygène et système pour la production d'énergie électrique |
US10822234B2 (en) | 2014-04-16 | 2020-11-03 | Praxair Technology, Inc. | Method and system for oxygen transport membrane enhanced integrated gasifier combined cycle (IGCC) |
WO2016057164A1 (fr) | 2014-10-07 | 2016-04-14 | Praxair Technology, Inc | Membrane de transport d'ion oxygène composite |
US10441922B2 (en) | 2015-06-29 | 2019-10-15 | Praxair Technology, Inc. | Dual function composite oxygen transport membrane |
US10118823B2 (en) | 2015-12-15 | 2018-11-06 | Praxair Technology, Inc. | Method of thermally-stabilizing an oxygen transport membrane-based reforming system |
US9938146B2 (en) | 2015-12-28 | 2018-04-10 | Praxair Technology, Inc. | High aspect ratio catalytic reactor and catalyst inserts therefor |
JP2019513081A (ja) | 2016-04-01 | 2019-05-23 | プラクスエア・テクノロジー・インコーポレイテッド | 触媒含有酸素輸送膜 |
JP6782106B2 (ja) * | 2016-07-05 | 2020-11-11 | 日本特殊陶業株式会社 | 改質装置 |
US11136238B2 (en) | 2018-05-21 | 2021-10-05 | Praxair Technology, Inc. | OTM syngas panel with gas heated reformer |
US11761096B2 (en) * | 2018-11-06 | 2023-09-19 | Utility Global, Inc. | Method of producing hydrogen |
US11289650B2 (en) * | 2019-03-04 | 2022-03-29 | International Business Machines Corporation | Stacked access device and resistive memory |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6033632A (en) | 1993-12-08 | 2000-03-07 | Eltron Research, Inc. | Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them |
WO2003089117A1 (fr) | 2002-04-18 | 2003-10-30 | Trustees Of Boston University | Separation d'hydrogene utilisant des membranes conductrices mixtes d'oxygene et d'ions-electrons |
Family Cites Families (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH441776A (de) | 1966-05-17 | 1967-08-15 | Marincek Borut | Verfahren zur Herstellung von Metallen durch Schmelzflusselektrolyse von Oxiden |
US4108743A (en) | 1977-05-02 | 1978-08-22 | Ford Motor Company | Method and apparatus for separating a metal from a salt thereof |
CA1203950A (fr) | 1982-12-23 | 1986-04-29 | Harold S. Cox | Articles a l'epreuve de l'electricite statique |
US6287432B1 (en) | 1987-03-13 | 2001-09-11 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
US5714091A (en) * | 1987-03-13 | 1998-02-03 | The Standard Oil Company | Process for the partial oxydation of hydrocarbons |
US5306411A (en) | 1989-05-25 | 1994-04-26 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
US4804448A (en) | 1987-06-24 | 1989-02-14 | Eltron Research, Inc. | Apparatus for simultaneous generation of alkali metal species and oxygen gas |
US4908113A (en) | 1987-09-01 | 1990-03-13 | Institute Of Gas Technology | Apparatus for the electrochemical separation of oxygen |
US4865925A (en) | 1987-12-14 | 1989-09-12 | Hughes Aircraft Company | Gas permeable electrode for electrochemical system |
CA2012009C (fr) | 1989-03-16 | 1999-01-19 | Tadashi Ogasawara | Procede pour la production electrolytique du magnesium |
JP2882104B2 (ja) * | 1991-07-17 | 1999-04-12 | 松下電器産業株式会社 | プロトン伝導体およびその製造方法 |
US5380467A (en) | 1992-03-19 | 1995-01-10 | Westinghouse Electric Company | Composition for extracting oxygen from fluid streams |
US5478444A (en) * | 1992-05-11 | 1995-12-26 | Gas Research Institute | Composite mixed ionic-electronic conductors for oxygen separation and electrocatalysis |
US5616223A (en) * | 1992-05-11 | 1997-04-01 | Gas Research Institute | Mixed ionic-electronic conducting composites for oxygen separation and electrocatalysis |
US5273628A (en) | 1992-05-11 | 1993-12-28 | Gas Research Institute | Mixed ionic-electronic conductors for oxygen separation and electrocatalysis |
US5509362A (en) | 1992-12-11 | 1996-04-23 | Energy And Environmental Research Corporation | Method and apparatus for unmixed combustion as an alternative to fire |
US5312525A (en) | 1993-01-06 | 1994-05-17 | Massachusetts Institute Of Technology | Method for refining molten metals and recovering metals from slags |
US5447555A (en) | 1994-01-12 | 1995-09-05 | Air Products And Chemicals, Inc. | Oxygen production by staged mixed conductor membranes |
US5520799A (en) | 1994-09-20 | 1996-05-28 | Mobil Oil Corporation | Distillate upgrading process |
DE69630702T2 (de) | 1995-04-25 | 2004-09-30 | Energy And Environmental Research Corp., Irvine | Verfahren und System zur Wärmeübertragung mit Hilfe eines Materials für die unvermischte Verbrennung von Kraftstoff und Luft |
US5962122A (en) | 1995-11-28 | 1999-10-05 | Hoechst Celanese Corporation | Liquid crystalline polymer composites having high dielectric constant |
US5976345A (en) | 1997-01-06 | 1999-11-02 | Boston University | Method and apparatus for metal extraction and sensor device related thereto |
US6162334A (en) | 1997-06-26 | 2000-12-19 | Alcoa Inc. | Inert anode containing base metal and noble metal useful for the electrolytic production of aluminum |
US6165553A (en) | 1998-08-26 | 2000-12-26 | Praxair Technology, Inc. | Method of fabricating ceramic membranes |
US6153163A (en) * | 1998-06-03 | 2000-11-28 | Praxair Technology, Inc. | Ceramic membrane reformer |
US6296687B2 (en) * | 1999-04-30 | 2001-10-02 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Hydrogen permeation through mixed protonic-electronic conducting materials |
US6235417B1 (en) * | 1999-04-30 | 2001-05-22 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources | Two-phase hydrogen permeation membrane |
US6471921B1 (en) | 1999-05-19 | 2002-10-29 | Eltron Research, Inc. | Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing |
US6146549A (en) | 1999-08-04 | 2000-11-14 | Eltron Research, Inc. | Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties |
US6541159B1 (en) | 1999-08-12 | 2003-04-01 | Reveo, Inc. | Oxygen separation through hydroxide-conductive membrane |
US20040157075A1 (en) * | 2000-06-09 | 2004-08-12 | Building Materials Investment Corporation | Single ply thermoplastic polyolefin (TPO) roofing membranes having superior heat seam peel strengths and low temperature flexibility |
US6677070B2 (en) | 2001-04-19 | 2004-01-13 | Hewlett-Packard Development Company, L.P. | Hybrid thin film/thick film solid oxide fuel cell and method of manufacturing the same |
US6726893B2 (en) * | 2002-09-17 | 2004-04-27 | The University Of Chicago | Hydrogen production by high-temperature water splitting using electron-conducting membranes |
US7229537B2 (en) * | 2003-07-10 | 2007-06-12 | Praxair Technology, Inc. | Composite oxygen ion transport element |
US7258820B2 (en) * | 2004-03-05 | 2007-08-21 | Ceramatec, Inc. | Ceramic mixed protonic/electronic conducting membranes for hydrogen separation |
AU2005294472A1 (en) * | 2004-10-05 | 2006-04-20 | Ctp Hydrogen Corporation | Conducting ceramics for electrochemical systems |
US20060234098A1 (en) | 2005-04-18 | 2006-10-19 | Clean Coal Energy, Llc | Direct carbon fuel cell with molten anode |
US20070245897A1 (en) * | 2006-04-20 | 2007-10-25 | Innovene Usa | Electron, hydrogen and oxygen conveying membranes |
-
2005
- 2005-10-21 EP EP05858461A patent/EP1814646A2/fr not_active Withdrawn
- 2005-10-21 JP JP2007543065A patent/JP2008520426A/ja not_active Withdrawn
- 2005-10-21 US US11/255,650 patent/US7588626B2/en not_active Expired - Fee Related
- 2005-10-21 WO PCT/US2005/038081 patent/WO2007011401A2/fr active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6033632A (en) | 1993-12-08 | 2000-03-07 | Eltron Research, Inc. | Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them |
WO2003089117A1 (fr) | 2002-04-18 | 2003-10-30 | Trustees Of Boston University | Separation d'hydrogene utilisant des membranes conductrices mixtes d'oxygene et d'ions-electrons |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007148057A1 (fr) * | 2006-06-21 | 2007-12-27 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Membrane de séparation de l'oxygène |
JP2008247649A (ja) * | 2007-03-29 | 2008-10-16 | Tdk Corp | 複合型混合導電体 |
Also Published As
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US20060191408A1 (en) | 2006-08-31 |
WO2007011401A3 (fr) | 2007-04-12 |
US7588626B2 (en) | 2009-09-15 |
JP2008520426A (ja) | 2008-06-19 |
EP1814646A2 (fr) | 2007-08-08 |
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